Mineral aggregate bonding compositions



Patented Sept. 20, 1949 MINERAL AGGREGATE BONDING COMPOSITIONS Arthur B. Hersberger, Drexel Hill, and Frank Gozlow, Philadelphia, Pa., assignors to The Atlantic Refining C0., Philadelphia, Pa., a corporation of Pennsylvania No Drawing.

Ihis invention relates to improved mineral aggregate bonding compositions and more particularly to the preparation of improved road paving compositions.

The two methods generally'used in the preparation of bituminous pavements are, one in which a layer of bituminous cut-back or emulsion is spread on a road, a layer of mineral a gregate such as crushed stone is spread upon it, and the mixture is compacted; and the other method is one in which mineral aggregate isfirst provided with a coating of bitumen by mixing the aggregate mechanically with a bitumen or bituminous cut-back or emulsion until an adhesive coating of the bitumen is formed on each piece of the aggregate, the coated aggregate then being laid on the road and compacted. Where aggregate isused hot bitumen or bituminous cut-back applied to the aggregate, there is little difficulty experienced in securing 'a good bond between the bitumen and the aggregate, except with an acidic aggregate such as siliceous aggregates.

One of the objects of the present invention is to permit thecoating of surfaces of damp or wet aggregates with a bituminous composition in such a manner that the coating obtained is satisfactory and produces a firmly bonded mass.-

A further object of this invention is to prepare a paving mixture bonded with asphalt in which the asphalt coating, when applied to either dry or wet aggregate is not readily displaced or stripped when subjected to the action of water.

A still further object of this invention is 'to prepare a bitumen or bituminous mixturecontaining an anti-stripping or adhesive agent which is stable to heat over considerable periods, and which is particularly adapted for incorporalthat has first been dried: and g tion in bitumens, asphalts, and road oils which may be stored, transported, or applied at elevated temperatures.

The present invention relates to a method of improving the adhesivity of bitumen to not only alkaline stones, mite, but also to acidic or siliceous type of mineral aggregates. Not onlydry, but also wet asgregates may be successfully coated by the products of the present invention, andthe pavings thereby prepared will not disintegrate under the action of water. It will be understood that the invention is especially advantageous in its application to the coating of wet mineral aggregates with bitumen, bituminous cut-backs, and bituminous emulsions.

Since adhesiveness is a consequence of wetting such as limestone, slag, and dolo- Application February 6, 1947, Serial No. 720,962

9 Claims. (01. 106-2 73) power, it is important that-the wetting power of thebituminous binders toward the mineral aggregate be as high as possible. In the presence of moisture or water, adhesiveness depends upon I the respective wetting powers of water and the bituminous binder toward the mineral aggregate; if the wetting power of the water is higher than that of the binder, the former will displace the latter, and prevent the bituminous binder from adhering to the surface of the aggregate. It is, therefore, an object of this invention to improve the adhesivity of the bituminous material as hereinafter described. i

In accordance with the present invention, it has been found that the wetting power of bitumens for all types of mineral aggregates is. markedly improvedwby incorporating in the =bitu-,

men a relatively small quantity of a condensation product of a diamine with a compound from the group consisting of alkyl and alkenyl substituted succinic and succinamic acids, anhyldrides, and acid esters thereof.

bitumens in amounts of from 0.1% to 2.0% by weight, were found to be highly satisfactory in increasing the wetting poweror 'adhesivity of the bitumens for aggregates. While larger quantities, for example, 5% to 10% of these products may be used, the improvement in 'adhesivity is not increased proportionately, and it appears to be uneconomical in most cases to use more than about 2% by weight of the products. Generally, from 0.5% to 2% will suffice, except under conditions in which the aggregate is exception-ally wet. The condensation products of this invention are soluble in or compatible with bituminous materials such-as petroleum asphalts or residuums, flux asphalts, coal tar pitches or residuums, cracking still tars or residues, as Well as heavy naphthenic or aromatic oils, and the like. In accordance with the present invention, the products may be incorporated in various bituminous These condensationproducts, when added to in order to render the. less'liable to strip from olefins such as propylene, butylene, isobutylene, the amylenes, and the hexylenes or mixtures thereof, are caused to react with an unsaturated dicarboxylic acid or anhydride under the influence of heatto produce the alkenylrdicarboxylic acid or arrhydrid'e. Suitable charge materials include maleic anhydride or acid, Iumaric acid, citraconic anhydride or acid, itacom'c anhydrideit; or acid, mesaconic acid, glutaconicanhydride or c acid, methyl itaconic anhydride oracid;'andnthetlfl" acid ester With an alkali metal alcoholate in a-lco- 1101 to replace a hydrogen atom ongthezalphaccara bon atom of the ester with an alkali metal atomiar, and then reacting this product with an alkyl.

halide to introduce the alkyl group and eliminatethe alkali metal as alkali metal halide. The alkylated' dlearlooxylic ester may then be reduced to the acid -or a the anhydrid'em Another 4 method for producing the C5 to:C--a1kyl dicarboxylicwacid oranhydride= comprises treating an unsaturated dicarboxylic acid-or anhydrid'ewith a hydrogen halide to obtain "a halogenatedgsaturated idicarboxylicacid 'or' anhydride and then replacing the halogen atom onthealpha carbon. atom with an alkyl group by treatmenawith an alkyl halide 1 and a eatalys tor an alkali metal.

Th'e alkyl or alkenyl dicarboxylic acid or anhydrid'e maythen bereactedz-with a diamineor-polyamine to obtain a condensation productsuitable'i. as an add itiv'e :fo'r Lbitumens. The diaminessor poly'amines nmay :.-be;.employed:in. molar ratios; 3

ranging fromi -l to :2,*although higher ratios are: not' detrimentalea MolarratiossotclB to 2 have :1 given very goo d" results: the production act: the s: condensation productsw The amines which :.may J boxylic acid. This product, when acidified with a mineral acid, such as hydrochloric acid, yielded the amido carboxylic acid, which in turn, may be condensed with a diamine by stirring the mixture at ordinary temperature, heat being ,liberated as thecondensation lproceedsu The reaction temperature may rise to 120 F.220 E, and upon cooling, the condensation products range from extremely ,viscous yellow-orange liquids to waxlike'; solids'f' Condensation products also suitable for use in accordahce'with :thi's'invention may be prepared by reactirrg the acid esters of the alkyl and alkenyl dicarboxylieacids or the acid esters of the alkyl and-alk'enyl amidecarboxylic acids with diamines orzpolyarninesl -.'Ihe:acid esters may be produced byilreacting, for example, equimolar quantities of an alcohol with the acid or anhydride. The

alcohols-may be exemplified by methyl, ethyl,

propyl, isopropyl, butyl, amyl, etc. The reactants maly be heated ;to itempieratures; ofcthe :order 'of 300 =-F. "and -'maintainedsat this: temperature,::for-e 1 to' 3 hours; sandsth-enrlistilled to recover the de sired acid ester. Another method fortpreparinglg the; acidi esters consists-tin :reacfinggafor example,

equimolar, quantitiesof the acid orianhydride'ande an alkali; metal: alcoholate by refluxing the mix-e, ture at:an:elevatedtemperature for 2 to -8 hoursa inutherpresen'ce; of 1a :diluentsuoh; asvbenzenew .:After-.refluxing, the alkalirma y :Jbe. aremoved by Washingthe productrwith :mineral: acid-,uand then.- separating, ithegbenzene -by=,;:di-stil1ation'; leaving; thedesired acid ester. To .preparethe condenser-. tion product; itequiamo-lar; quantities; :for; example, 7. or a idiaminezand theracidesterzare mixedrateor dinar-y temperature; sand- :thenyigQ1-0.usly:stirred .& Asthe:,condensati0n- :progresses, the temperature may 7' rise :to 1120.5 :Fe ISOPiEE; and": after 1coo1ing;- there'ris 'obtained a condensation product WhiChri be utiliz'edi n:thecondensationreaction are-those .4mimayrange from1a yis'couszoiltoa solid.: 1

containingiromfi 60.18 carbon atoms, and may be. exemplified by ethylenetdia mine,:diethylene tria minei triethylene .tetraminea: l-methyl: :ethyle'ne diamine; -"l-ethyl ethylene diamine,=.-propylene1-diae mine; butyle'ne :diamine; trimethylv trim ethylene-145,

diaminae.tetram'ethylenetzdiamine,* diaminbpene: ta-ne: or ipentamethylene diamina diaminohexane, hexamethyl'eneii diamine, 1 heptamethylene: dia-r; mine; diaminmoctanen .decamethylene: ediamine,

and the higher homologues' upztorl8 carbon aton1s',.t.{-O

phenylenetdiamine, the alkylated phenylene; dia-ei. mines' having nuclearzsubstituents such as-methyl; ethylg propylg butylg etcrx naphthalene -diamine,;i. and- -'-the'--= alkylated naphthalene I diaminesnzl The;

condensation reaction may be carried out by simply addin g diamine: or :polyamine to thel alkyla': or alkenyl dicarboxylic: acid .or: anhydridenat. orl-s dmarytemperature ifio F. 'to.-803 FE)" andv thena. stirring zvigorouslya; As.. the condensation pro-a;

ceeds, the temperature .ofxthe reaction.-mixture/.6011.

rises to 21510311523220? Faiwith the elimination ;of;: water: produced \by the condensation. 'Ihezconev densation iprod-ucts; when ."cooled .:toi, room,; tem-:- penatureprange from viscous; yellowishzliquids'to,i

solids: When :thelcharger materialszzare them selves solids, the reaction may.tbezxinitiated;cbym the :apphcatiorrzofi heatsrsufiicientr to render-the reactants :liquid and capable of being; mixed and stirred;v

In the preparation of the condensatiomprodnctfli).

totiform: theaamanoniumt salt of the-@ami-do :CaI' -wi The present invention mayilbELiUEthEP'lHLISt'I'Ht-c-' ed :"bysthe:ifollowingnexamples, .;wh ich-; iinowevere:v are not to be construed'nasf limiting -the.scope,e therecfzr;

1.: N onylene, r. dodecylene;, and octadecylene -,-zwere reactedcrespectivel3t,-:With ;maleic anhydride; =7 by heatingz :at: 400 1:F.';-i11 {a :closed system with no externa'lgpressure.- applied; for a .perio'dwpf- 1 to 4 1- hours. Vacuum-distillation 0t thereactionlproducts :yielded thev respective. vnonenyl, dodecenyl, andioctadecenyl; 'Succinic anhydrides-,-substantial-. ly. a'frleevoflvaunreacted ,zmono-clefinsl sand maleic anhydrides; Using' equimolare proportions of the monoolefi-nnand the maleicnanhydride gave .a 40%; to 460%; yield -,of :the corresponding alknyl succini-c anhydridea Wl 1ereas,-using 4 molesofj monorolefi -n -to, 1 ,mole of 1 maleic .anhydridel gave .l substantially aconversion, into ,the. .cOrre-M. spending al-kenyL-succinie anhydridel,

Th'ewalkenylpsuccinic, anhydrides as, above .pre: pared were condensed with ethylene diam'inebyj slowly add-ing; 2 lmoles rof the diam-ineltolthel re speotive .anhydrides;l-ataroom temperature .with ,1 vigorouststirring. ,Reaction immediately. occurred T and the temperature of the reaction mixture rose;

sand; in hydrocarbon-solvents employed. in prel paring lcuteback vaspl altsvor. road .,oils'.\

2. To-l moleoteachof the nonenyl, dodec'en'yl, and,pctadecenyhsuccinic anhydrides was. added 4 L moles of ammonia (28% NHs in water solution);

with avigoronslstirring, ,and .lcooling with icel water,

Heat was liberated and viscous solutions of :the

corresponding ammonium alkenyl succinamates in excess ammonia were obtained. Each of the solutions was diluted with water and cooled to 32 F., and a 20% concentration hydrochloric acid solution was slowly added with stirring until two phases appeared, and the lower or aqueous phase was acidic to methyl orange indicator. The upper phase was a viscous yellow oil which was .separated from the acid aqueous phase, and which constituted the alkenyl succinamic acid. An alternative method for the preparation of the alkenyl succinamic acids comprised heating 1 mole of the alkenyl succinic anhydride to 350 F.-400 F. and maintaining the anhydride at this temperaturewhile passing gaseous ammonia through the anhydride. After 2 to 3 rnoles oi ammonia had been added, the product was quickly cooled and the alkenyl-succinimide, which was a liquid, was obtained. 1 mole of sodium hydroxide in water solution was added to the succinimide with stirring to give a water solution of the sodium salt of the alkenyl succinamic acid; Acidification of the sodium salt solution liberated the alkenyl succinamic acid as a viscous yellow oil. I

The condensation of, the; alkenyl succinamic acid with ethylene diamine was effected by slowly 1 mole ofan-alkali metal alcoholate, such as sodium ethylate, in the presence of benzene for 2 to 8 hours. The alkali may be removed by washing the product with mineral acid, and the benzene removed by distillation, leaving the acid ester of 'the alkenyl succinic anhydride.-

The condensation products prepared asabove described were tested as adhesivity agents for bitumens in the following manner.

Acut-back asphalt was prepared by mixing 75%of an 85-100 penetration steam reduced petroleum asphalt with of blending naphtha To samples of,

(boilingrange 200 F.350 F.). this cut-back asphalt were added small amounts (0.1% to 1%) of the various condensation products, and-the resulting cut-backs were admixed in small amounts (6%) at 180 F. withmineral rotated for 15 minutes at R. P. M. at 80 F.

and the percent coating again noted. Theresults are presented in the following table.

Per cent Coated M l li ergeng fill-aims cuto e ro uc ac per 100 Condensatwn Product Ratio added to grams Rhyo- Before After cut-back lite water water test test Nonenyl succinic anhydridecthyl n diamine 3 8 3g 0. 10 6.0 85 Dodegenyl inic anhydndecthylene diamine 1:2 0. 50 6. 0 90 90 I 1.00 6.0 100 100 o. 10 6. 0 6O Octadecenyl succinic anhydnde-ethylene diamine 1:2 g. (5)8 6. 0 80 6. 0 90 Nonenyl succinamic acid-ethylene diaminen 1:1 1- 00 7- 0 90 90 0. 10 6. 0 75 e0 Dodecenyl succmamlc acid-ethylene diamine 1:1 0. 50 6.0 90 90 1. 00 6. 0 100 90 0. l0 6. 0 75 60 o tadecenyl uccinamic acid-ethylene diamine 1:1 0. 50 6. 0 90 90 1. 00 6. 0 90 90 0. 10 6.0 so 40 Ethyl hydrogen dodecenyl succmate-ethylene diamine..." 1:1 0. 60 6. 0 95 1. 00 6. 0 100 Nrmn 6. 0 80 30 adding 1 mole of the diamine to 1 mole of the alkenyl succinamic acid with vigorous stirring at room temperature. During the ensuing reaction, the temperature rose to F.220 F., and upon cooling, there was obtained a viscous yellow liquid, almost wax-like, which was water soluble and soluble in hydrocarbon solvents (aromatic naphtha, kerosine, or tar distillate), as well as in asphalt.

3. The condensation of the alkenyl succinic acid esters with ethylene diamine was accomplished by mixing equimolar proportions of the acid ester and the diamine at room temperature with vigorous stirring. Due to the reaction, a temperature rise to 120 F.-180 F. was observed, and the resulting condensation product, upon cooling, was an extremely viscous oil which was soluble in water and aromatic hydrocarbon s01- vents. The acid esters used in this condensation reaction may be prepared by the reaction of equimolar proportions of alcohol, for example, methyl or ethyl, with the alkenyl succinic anhydride. The reactants are heated to 300 F. and maintained at this temperature for 1 to 3 hours, and then distilled to recover the alkenyl succinic acid ester. Alternatively, 1 mole of alkenyl succinic anhydride, for example, dodecenyl succinic anhydride, may be refluxed with From the data above given, it will be evident that the addition of small amounts of condensation products of diamines with substituted succinic and succinamic acids, and acid esters thereof, markedly enhance the adhesivity of bitumens for mineral aggregates, as compared with bitumins containing no additive.

We claim:

1. A mineral aggregate bonding composition comprising a bitumen and a condensation product of a diamine with a compound from the group consisting of alkyl and alkenyl substituted succinic and succinamic acids, anhydrides, and acid esters thereof, such condensation product being present in an amount suflicient to substantially increase the adhesivity of the bitumen for mineral aggregates.

2. A mineral aggregate bonding composition comprising asphalt and a condensation product of a diamine with a compound from the group consisting of alkyl and alkenyl substituted succinic and succinamic acids, anhydrides, and acid esters thereof, such condensation product being present in an amount sufficient to substantially increase the adhesivity of the asphalt for mineral aggregates.

3. A mineral aggregate bonding composition comprising a cut-back asphalt and a condensa- The,

zgz-xsagases.

tion product 'of aidi'amine: Withca GOIIIDOUIldJ-fFOIIli the groupconsisting of 'al-kyl a'ndl' alke'nyltsube stituted succinic and succina'niic acids; anhydrides, and. acid esters thereof, .fSH'C'h icondensationproduct being preseritiniamamDunt suffi cient to substantially:increaseitlre adhesivity*df the out-back asphal t for rriineraI aggnegates 4. A "mineral aggregate bonding-compositions; comprising a bitumen -and from 0.1% to 2 %iof4a1 condensation product 05 a diet-mine With-acornpound fr'om the group c'onsisting of alkylc and T alk'enyl :subs'titute'd :succi'nic. and: :succina'niim acids, anhydrides, -and=acid' esters thereof.

5. A' mineral aggregate bonding composition comprising a :bitumen'and from- 05 1 t'o 2% of a condensation product of adiamine: :CDl'itZiLiIli-Ii'g from 2to 18 carbon atoms with amompoiindfrom th'e group consisting f alk-yl -and alkeriyl: substituted succini'c and s'u'ccinami'c: acids}: an

hydrides, and acid esters thereof.

6; A minera1 aggregate bonding composition comprising-a bitumenand' from -0.1% to-2%"'of a condensation product of a diamine containingfrom 2 to l-Bcarbon atoms with'a compound from the group consisting of al-k yl and alkenyl substituted succinic and 'succinamic acids, 'anh ydrides, and acid'esters thereof, saida'lk s'rl and alkenyi substituents containing from" 13020 car bon atoms.

7. -A-- mineral aggr'egate bondinacomposition compfiising caibitumenfiandfiirom 20.5% to of ia i condern'sation':produc'irx off ethylene diamine: ands nonen yl succinicsacid anhydride;:

"8. @A mineral aggregate bonding compositio'n'. comprising'ia-zbitumeri and from: 0.51% to. 2% or "a condensation: :I product 1' of ethylene 'di'amine: and? nonenyl succinamic acid.

9;' A mineral aggregate bonding "composition comprising" a' bitumen and 'from-r0;5% to 2% of:

101 arcondensation: iproducti-of ethylene diamine sand 1 ethyl hydrogen: dodecenyl sucoinate.

HERSBERGER. J GOZLOW.

REEERENCES -GITED 7 The following references are 'of record inthe" I of th'is -'patent:

' UNI'I'EDSTATESi-PA'I'ENTS 

